Dyeing human hair with oxidation dyes and arginine or a protamine protein

ABSTRACT

Oxidation hair dyeing compositions containing a peroxide source, one or more oxidation dye precursors and arginine or a protein or polypeptide having a high arginine content as essential components.

United States Patent 1191 Milbrada [4 1 Jan. 21, 1975 [54] DYEING HUMAN HAIR WITH OXIDATION DYES AND ARGININE OR A PROTAMINE PROTEIN 75] Inventor: Edward J. Milbrada, Cincinnati,

Ohio

'[73] Assignee: The Proctor & Gamble Company,

Cincinnati, Ohio 221 Filed: Mar. 30, 1971 21 Appl.No.: 129,557

. 8/32 [51] Int. Cl A6lk l/l2 [58] Field of Search 8/102, 11, 32

[56] References Cited UNITED STATES PATENTS 3,200,040 8/1965 Lange 8/l0.2 X

OTHER PUBLICATIONS Hackhs Chemical Dictionary, The Blakiston Co., Philadelphia, Pa., (1944), p. 690.

Primary Examiner-Albert T. Meyers Assistant Examiner-Vera C. Clarke [57] ABSTRACT Oxidation hair dyeing compositions containing a peroxide source, one or more oxidation dye precursors and arginine or a protein or polypeptide having a high arginine content as essential components.

16 Claims, No Drawings DYEING HUMAN HAIR WITH OXIDATION DYES AND ARGININE OR A PROTAMINE PROTEIN BACKGROUND OF THE INVENTION forming" the oxidation a'fH fi concentrations a 315E cent or more and a pH of 8.5 or higher for time periods in excess of 20 minutes) and high concentrations of dye precursors to produce the desired coloration. For these and other reasons, such dyes can cause skin irritation and sensitization as well as hair damage to some users. Further, the ammonium hydroxide which is generally used to maintain the high pH in these products has an odor which is offensive to most users and is thought to contribute to hair damage and skin irritation and sensitization. Furthermore, even after subjecting the hair to the presently availableoxidation dyes the resulting hair colors are often rather unstable and are partially removed by shampooing. I

It is an object of this invention to provide an improved oxidation hair dye composition suitable for use on growing hair which is essentially ordorless and which leaves the hair colored with shampoo-stable dyes. It is a further object to provide an improved process for coloring hair using oxidation hair dye compositions comprising arginine or a protein or polypeptide of the type herein disclosed, a peroxide and various oxidation dye precursors. These and other objects are obtained by this invention as will become apparent from the following disclosure. The concurrently filed application of Milbrada, entitled Oxidation Hair Dyes and Process," Ser. No. 129,556, filed Mar. 30, 1971, now abandoned, relates to the use of guanidinium salts in hair dye compositions. The concurrently filed applications of Knohl and Zeffren, entitled Hair Bleaching Compositions," Ser. No. 129,555, filed Mar. 30, 1971, now abandoned, and Hair Bleaching Compositions, Ser. No. 129554, filed Mar. 30, 1971, now abandoned, relate to the use of peroxide in combination with guani dine salts, arginine and arginine-containing proteins to bleach hair.

SUMMARY OF THE INVENTION The present invention relates to improved oxidation dye compositions for the coloring of hair comprising various oxidation dye precursors, a peroxide, and arginine, or proteins or polypeptides having a high arginine content, and a process for coloring hair using same.

More specifically, the present invention encompasses oxidation hair dye compositions comprising: (1) from about 0.1 percent to about 20 percent by weight of a compound selected from the group consisting of arginine, and protamine proteins and polypeptides containing a major proportion (50 percent, by weight, and greater) of arginine. units in.their structure, and the peroxide-compatible salts thereof; (2) from about 0.001 percent to about 6 percent by weight of one or more oxidation dye precursors, e.g., compounds se- 2 lected from the group consisting of:

R N R N R 11 and R OR wherein Y is selected from the group consisting of hydrogen, halogen, nitro, amino, hydroxyl,

and SO M where M is hydrogen, alkali or alkaline earth metal, ammonium or substituted ammonium wherein one or more hydrogens on the ammonium ion is replaced with a l to 3 carbon atom alkyl or hydroxyalkyl radical, R R R and R are the same or different from each other and are selected from the group consisting of hydrogen, C to C alkyl and alkenyl and C to C aryl, alkaryl, and aralkyl, R is selected from the group consisting of hydrogen, C, to C unsubstituted or substituted alkyl and alkenyl wherein the substituents are selected from those designated as Y, and C to C unsubstituted or substituted aryl, alkaryl and aralkyl wherein the substituents are selected from those designated as Y, and R is selected from the group consisting of hydrogen, and C to C substituted or unsubstituted alkyl and alkenyl wherein the substituents are those defined as Y, and the peroxide-compatible salts thereof; and (3) from about 0.1 percent to about 6 percent by weight of a water-soluble peroxide compound. The compositions herein are formulated as liquids at a pH (aqueous) of about 8 to about 11 prior to application to the hair.

In addition, this invention encompasses a process for coloring hair, especially growing human hair, comprising contacting said hair with a composition comprising arginine or a protein or polypeptide containing a major amount of arginine, or the peroxide-compatible salts thereof, one or more oxidation dye precursors and a water-soluble peroxide compound, at a pH (aqueous) of from about 8 to about 1 1, all as disclosed herein, and allowing the color to develop (usually 2 to about 60 minutes).

DETAILED DESCRIPTION OF THE INVENTION The dyeing compositions of this invention are employed on the hair at an optimum pH of from about 8 to about 11, more preferably about 9 to about 10. Although this pH is in the normal range of hair dyeing compositions, an unexpected increase in the stability of the resulting hair dyes is noted with the present compositions. While not intending to be restricted by theory, it is hypothesized that the arginine or proteins used herein enhance the penetration of the dye precursors into the hair shaft, thereby stabilizing the dye molecules formed by oxidation. Whatever the reason for the improved hair dyeing properties of the present compositions, the improvement is not attributable merely to the pH, but is related to the presence of the arginine compound.

The amino acid, arginine, or its peroxide-compatible salts, as hereinafter detailed, is one essential component of the dyeing compositions of this invention. Alternatively, proteins or polypeptides having a high arginine content can be used herein in place of arginine to provide the enhanced dyeing activity. The pure amino acid, the proteins, the polypeptides containing a major proportion of arginine units, and their respective salts are referred to collectively herein as arginine compounds. Proteins having a major proportion of arginine units in their structures are members of that class of proteins known as protamines. While it is not possible to specify with certainty the complete structures of each member of this class since few of their amino acid sequences have been determined, the protamine proteins all have several common characteristics. The most distinctive features of this class of proteins are: (a) a low molecular weight, in the range of about 5,000; (b) a high isoelectric point, in the pH range of about to 12; and (c) a high arginine content, in the range from about 50 percent to about 90 percent, by weight, of the total protein. Protamine proteins having a high arginine content suitable for use herein are listed in R. J. BLock and K. W. Weiss, Amino Acid Handbook," Thomas, Springfield, Illinois (1956), page 260, et seq. Some of the protamine proteins of high arginine content suitable for use herein include: clupein, obtainable from herring; fontinin, obtainable from salmon; salmin, obtainable from salmon, iridin, obtainable from rainbow trout; lacustrin, obtainable from sea trout; gallin, obtainable from fowl; sturin, obtainable from sturgeon; sperm nucleoprotein from mollusks (Patella coerulea); and macerated bovine testes. All of the above proteins of the protamine class have an arginine content greater than 50 percent and are suitably employed herein.

Proteins of the type hereinabove described can be subjected to acid or base hydrolysis to yield polypeptides which also have a high arginine content. Such polypeptides are obtained, for example, during the processing of fish and fowl and can be employed in the dyeing compositions of this invention. Again, the exact chemical structure of these polypeptides cannot be specified with certainty in that they have very complex amino acid sequences. As in the case of their parent proteins, which are protamines of the type hereinabove disclosed, the polypeptides useful herein have a molecular weight below about 5,000, are basic (pH 10-12), and have an arginine content of about 50 percent, or greater, by weight.

Since arginine and the protamine proteins and polypeptides having an arginine content of 50%, or greater, are basic, they are often isolated from natural sources in the form of salts. Such salts are suitable for use herein, if their anions are compatible with peroxides. Arginine salts, protamine protein salts and protamine polypeptide salts are formed by reacting these materials with mineral acids such as hydrochloric acid, phosphoric acid, carbonic acid, sulfuric acid, nitric acid, etc., and the organic acids such as formic acid, acetic acid, lauric acid, chloroacetic acid and the like, each of which provide anions which are compatible with peroxides. Acids containing metallo-anions and strongly reducing anions, e.g., chromic acid and hydrogen thiocyanate, are not suitable herein in that these anions react with the peroxide.

Reaction of the aforementioned arginine, protamines, etc., with the exemplary acids in appropriate amounts yields salts useful herein. For example. arginine chloride, arginine carbonate, arginine sulfate, salmin sulfate, clupein hydrochloride, iridin phosphate, lacustrin carbonate, gallin carbonate, sturin chloride, sperm nucleoprotein hydrochloride, arginine phosphate, acid hydrolyzed sturin pyrophosphate, arginine nitrate, base hydrolyzed gallin acetate, hydrolyzed lacustrin chloroacetate, and the like are suitable for use in the compositions of this invention.

The arginine, protamine protein, protamine polypeptides, and peroxide compatible salts thereof, are used herein at concentrations from about 0.1 percent to 20 percent, preferably 0.5 percent to about 4 percent by weight of the total dye composition. The phosphates and carbonate salts are preferred for this purpose in that they are self-buffering. Arginine phosphate, arginine carbonate and arginine chloride are preferred. Clupein carbonate and salmin phosphate are also pre ferred herein.

The oxidation dye precursors which are used in the compositions and processes herein include aromatic diamines, polyhydric phenols, amino phenols and derivatives of these aromatic compounds (e.g., N- substituted derivatives of the amines, and ethers of the phenols). In general terms, oxidation hair dye precursors include those monomeric materials which, on oxidation, form oligomers or polymers having extended conjugated systems of electrons in their molecular structure. Because of the new electronic structure, the resultant oligomers and polymers exhibit a shift in their electronic spectra to the visible range and appear colored. For example, oxidation dye precursors capable of forming colored polymers include materials such as aniline, which has a single functional group and which, on oxidation, forms a series of conjugated imines and guinonoid dimers, trimers, etc. ranging in color from green to black. Compounds such as pphenylenediamine, which has two functional groups, are capable of oxidative polymerization to yield higher molecular weight colored materials having extended conjugated electron systems, i.e., the so-called Bandrowskis Base type of dye compound. Color modifiers, such as those detailed hereinafter, can optionally be used in conjunction with the oxidation dye precursors herein and are thought to interpose themselves in the colored polymers during their formation and to cause shifts in the electronic spectra thereof, thereby resulting in slight color changes. A representative list of oxidation dye precursors suitable for use herein is found in Sagarin, Cosmetic Science and Technology, Interscience, pages 504 and 508. It is to be understood taht arginine and the protamine proteins, polypeptides and peroxide-compatible salts thereof, are suitable for use (in combination with a peroxide as detailed herein) with all manner of oxidation dye precursors and color modifiers and that the precursors detailed below are only by way of example and are not intended to limit the compositions and processes herein.

The typical aromatic diamines, polyhydric phenols, amino phenols, and derivatives thereof, described above as primary dye precursors can also have additional substituents on the aromatic ring, e.g., halogen, aldehyde, carboxylic acid, nitro, sulfonic acid and substituted and unsubstituted hydrocarbon groups, as well as additional substitutents on the amino nitrogen and on the phenolic oxygen, e.g., substituted and unsubstituted alkyl and aryl groups.

Examples of suitable aromatic diamines, amino phenols, polyphydric phenols and derivatives thereof, respectively, arecompounds having the general formulas (A), (B) and (C) below:

(A) N-R R or R N R N-R R HX wherein Y is hydrogen, halogen, (e.g., fluorine, chlorine, bromine or iodine), nitro, amino, hydroxyl,

O I CH -COOM or -SO M (where M is hydrogen or an alkali or alkaline earth metal, ammonium, or substituted ammonium wherein one or more hydrogens on the ammonium ion is replaced with a l to 3 carbon atom alkyl or hydroxyalkyl radical), wherein R,, R R and R are the same or different from each other and are selected from the group consisting of hydrogen, C to C, alkyl or alkenyl and C to C aryl, alkaryl or aralkyl, and R is hydrogen, C, to C unsubstituted or substituted alkyl or alkenyl wherein the substituents are selected from those designated as Y, above, or C to C unsubstituted or substituted aryl, alkaryl or aralkyl wherein the substituents are selected from those defined as Y, above. Since the precursors of formula (A) are amines, they can be used herein in the form of peroxide-compatible salts, as noted, wherein X represents peroxidecompatible anions of the type hereinbefore detailed. The general formula of the salt indicated is to be understood to encompass those salts having mono-, di-, and tri-negative anions. Specific examples of formula (A) compounds are:

o-phenylenediamine m-phenylenediamine p-phenylenediamine 2-chloro-p-phenylenediamine sulfate 2-iodo-p-phenylenediamine 4-nitro-o-phenylenediamine phosphate 2-nitro-p-phenylenediamine 1,3 ,S-triaminobenzene 6 2-hydroxy-p-phenylenediamine 2,4-diaminobenzoic acid sodium 2,4-diaminobenzoate calcium di-2,4-diaminobenzoate ammonium 2,4-diaminobenzoate trimethylammonium 2,4-diaminobenzoate tri-(2-hydroxyethyl)ammonium 2,4-diaminobenzoate 2,4-diaminobenzaldehyde carbonate 2,4-diaminobenzenesulfonic acid potassium 2,4-diaminobenzenesulfonate N,N-diisopropyl-p-phenylenediamine bicarbonate N,N-dimethyl-p-phenylenediamine N-methyl-N'-(2-propenyl)-p-phenylenediamine N-phenyl-p-phenylenediamine chloride N-phenyl-N-benzyl-p-phenylenediamine N-ethyl-N'-(3-ethylphenyl)-p-phenylenediamine 2,4-toluenediamine dinitrate 2-ethyl-pphenylenediamine 2-(2-bromoethyl)-p-phenylenediamine 2-phenyl-p-phenylenediamine laurate 4-(2,5-diaminophenyl)benzaldehyde Z-benzyl-p-phenylenediamine acetate 2-(4-nitrobenzyl)-p-phenylenediamine 2-(4-methylphenyl)-p-phenylenediamine 2-(2,5-diaminophenyl)-5-methylbenzoic acid where X and Y are the same as in formula (A), R, and R can be the same or different from each other and are the same as in formula (A), R is the same as in formula (A) and R is hydrogen or C to C substituted or unsubstituted alkyl or alkenyl wherein the substituents are selected from those defined as Y in formula (A). Specific examples of formula (B) compounds are: o-aminophenol m-aminophenol p-aminophenol 2-chloro-p-aminophenol 2-iodo-p-aminophenol 2-nitro-p-aminophenol 3 ,4-dihydroxyaniline 3,4-diaminophenol chloroacetate 2-hydroxy-4-aminobenzoic acid 2-hydroxy-4-aminobenzaldehyde 3-amino-4-hydroxybenzenesulfonic acid N,N-diisopropyl-p-aminophenol N-methyl-N-( l-propenyl )-p-aminophenol N-phenyl-N-benzyl-p-aminophenol sulfate N-methyl-N-(3-ethylphenyl)-p-aminophenol 2-nitro-5-ethyl-p-aminophenol 2-nitro-5-(2-bromoethyl)-p-aminophenol (2-hydroxy-5-aminophenyl)acetaldehyde 2-methyl-p-aminophenol (2-hydroxy-5-aminophenyl)acetic acid 3-(2-hydroxy-5-aminophenyl)-l-propene 3-(2-hydroxy-5-aminophenyl)-2-chloro-l-propene 2-phenyl-p-aminophen0l palmitate 2-(4-nitrophenyl)-p-aminophenol 2-benzyl-p-aminophenol 2-(4-chlorobenzyl)-p-aminophenol perchlorate 2-(4-methylphenyl)-p-aminophenol 2-(2-amino-4-methylphenyl)-p-aminophenol p-methoxyaniline 2-bromoethyl-4-aminophenyl ether phosphite 2-nitroethyl-4-aminophenyl ether bromide Z-aminoethyl-4-aminophenyl ether 2-hydroxyethyl-4-aminophenyl ether (4-aminophenoxy)acetaldehyde (4-aminophenoxy)acetic acid (4-aminophenoxy)methanesulfonic acid l-propenyl-4-aminophenyl ether isobutyrate (2-chloro)-l-propenyl-4-aminophenyl ether (2-nitro)-l-propenyl-4-aminophenyl ether (2-amino) -1-propenyl-4-aminophenyl ether (2-hydroxy)-l-propenyl-4-aminophenyl ether R5 OR where Y, R, and R are as defined above in formula (B). Specific examples of formula (C) compounds are:

o-hydroxyphenol (catechol) m-hydroxyphenol (resorcinol) p-hydroxyphenol (hydroquinone) 4-methoxyphenol Z-methoxyphenol 4-(2-chloroethoxy)phenol 4-(2-propenoxy)phenol 4-(3-chloro-2-propenoxy)phenol 2-chloro-4-hydroxyphenol (2-chlorohydroquinone) 2-nitro-4-hydroxyphenol (2-nitrohydroquinone) 2-amino-4-hydroxyphenol 1,2,3-trihydroxybenzene (pyrogallol) 2,4-dihydroxybenzaldehyde 3,4-dihydroxybenzoic acid 2,4-dihydroxybenzenesulfonic acid 3-ethyl-4-hydroxyphenol 3-(2-nitroethyl)-4-hydroxyphenol 3-(2-propenyl)-4-hydroxyphenol 3-(3-chloro-2-propenyl)-4-hydroxypheno 2-phenyl-4-hydroxyphenol 2-(4-chlorophenyl)-4-hydroxyphenol 2-benzyl-4-hydroxyphenol 2-(Z-nitrophenyl)-4-hydroxyphenol 2-(2-methylphenyl)-4-hydroxyphenol 2-(2-methyl-4-chl0rophenyl)-4-hydroxyphenol 3-methoxy-4-hydroxy-benzaldehyde 2-methoxy-4-( l -propenyl)phenol 4-hydroxy-3-methoxycinnamic acid 2,5-dimethoxyaniline Color modifiers are optionally employed in the compositions and processes of this invention and include certain aromatic amines and phenols and derivatives thereof which do not produce color singly, but which modify the color, shade or intensity of the colors developed by the oxidation dye precursors. Certain aromatic amines and phenolic compounds, and derivatives thereof, including some aromatic diamines and polyhydric phenols of the types described by formulas (A), (B) and (C) above, but which are well known in the art not to be suitable oxidation dye precursors, are suitable as color modifiers herein.

The aromatic amines and phenols and derivatives described above as color modifiers can also have additional substituents on the aromatic ring, e.g., halogen, aldehyde, carboxylic acid, nitro, sulfonyl and substituted and unsubstituted hydrocarbon groups, as well as additional substituents on the amino nitrogen, or phenolic oxygen, e.g., substituted and unsubstituted alkyl and aryl groups. Again, peroxide-compatible salts thereof are suitable for use herein.

Examples of aromatic amines, phenols and derivatives thereof are compounds of the general formulas (D) and (E) below:

wherein Z is hydrogen, C, and C alkyhhalogen (e.g., fluorine, chlorine, bromine or iodine) nitro,

O in COOM or M, (where M is hydrogen or an alkali or alkaline earth metal, ammonium or substituted ammonium wherein one or more hydrogens on the ammonium ion is replaced with a 1 to 3 carbon atom alkyl or hydroxyalkyl radical), wherein R, and R are the same or different and are selected from the group consisting of hydrogen, C, to C, alkyl or alkenyl and C to C aryl, alkaryl or aralkyl and R is hydrogen, C, to C unsubstituted or substituted alkyl or alkenyl wherein the substituents are selected from those designated as Z above or C to C unsubstituted or substituted aryl, alkaryl or aralkyl wherein the substituents are selected from those defined as Z above and wherein X is as defined in formula (A). Specific examples of formula (D) compounds are: aniline p-chloroaniline sulfate p-fluoroaniline p-nitroaniline p-aminobenzaldehyde p-aminobenzoic acid sodium-p-aminobenzoate lithium-p-aminobenzoate calcium di-p-aminobenzoate ammonium-p-aminobenzoate trimethylammonium-p-aminobenzoate tri(2-hydroxyethyl)-p-aminobenzoate p-aminobenzenesulfonic acid potassium p-aminobenzenesulfonate N-methylaniline N-propyl-N-phenylaniline chloride N-methyl-N-2-propenylaniline N-benzylaniline N-(2-ethylphenyl)aniline 4-methylaniline 4-(2-bromoethyl)aniline 2-(2-nitroethyl)aniline (4-aminophenyl)acetaldehyde 4-amin0phenyl)acetic acid 4-( Z-propenyUaniline acetate 4-(3-bromo-2-propenyl)aniline 4-phenylaniline chloroacetate 4-(3-chlorophenyl)aniline 4-benzylaniline 4-(4-iodobenzyl)aniline 4-(3-ethylphenyl)aniline 4-(2-chloro-4-ethylphenyl)aniline wherein Z and R are defined as in formula (D) and R is hydrogen or C to C substituted or unsubstituted alkyl or alkenyl wherein the substituents are selected from those defined 'as Z in formula (D). Specific examples of formula (E) compounds are: phenol p-chlorophenol p-nitrophenol p-hydroxybenzaldehyde p-hydroxybenzoic acid p-hydroxybenzenesulfonic acid ethylphenyl ether 2-chloroethylphenyl ether 2-nitroethylphenyl ether phenoxyacetaldehyde phenoxyacetic acid 3-phenoxy-l-propene 3-phenoxy-2-nitro-l-propene 3'-phenoxy-2-bromo-1-propene 4-propylphenol 4(3-bromopropyl)phenol 2-(2-nitroethyl)phenol (4-hydroxyphenyl)acetaldehyde (4-hydroxyphenyl)acetic acid 4-(2-propenyl)phenol 4-phenylphenol 4-(3-bromophenyl)phenol 4-benzylphenol 4-(3-fluoro-2-propenyl)phenol 4-(4-chlorobenzyl)phenol 4-(3-ethylphenyl)phenol 4-(2-chloro-3-ethylphenyl)phenol 2,5-xylenol The oxidation dye precursors can be used herein alone or in combination with other oxidation dye precursors, and one or more dye precursors can be used in combination with one or more color modifiers. The choice of a single dye precursor or of a particular combination of dye precursors and modifers will be determined by the color, shade and intensity of coloration which is desired. There are eleven preferred oxidation dye precursors which can be used herein, singly or in combination, to provide oxidation hair dyes having a variety of shades ranging from ash blonde to black; these are: pyrogallol, resorcinol, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, oaminophenol, p-aminophenol, 4-amino-2-nitrophenol, nitro-p-phenylenediamine, N-phenyl-pphenylenediamine and 2,4-diaminoanisole. These can be used in the molecular form or in the form of peroxide-compatible salts, as detailed above.

The concentration of dye precursor (and color modifier, if used) in the coloring solution can be from about 0.001 percent to about 6 percent by weight and is preferably from about 0.01 percent to about 2.0 percent by weight.

A peroxide is required herein at a concentration of about 0.1 percent to about 6.0 percent by weight to develop the color. The peroxide component of the present compositions comprises hydrogen peroxide or any of the water-soluble alkali metal or alkaline earth metal peroxides such as sodium peroxide, potassium peroxide, and the like. In addition, peroxide complexes such as the water-soluble addition compounds of organic materials such as urea with hydrogen peroxide are suitable herein; examples of some of these materials include urea-peroxide, N-methylurea peroxide, and the like. Sodium perborate is also suitable herein as are the organic peroxides, e.g., the organic peroxy acids having the general formula RCOOOH, with R being lower alkyl and phenyl. Preferred are H 0 alkali metal peroxides and urea-peroxide.

As noted hereinabove, the dyes of this invention are used in the basic pH range (pH 8 to l 1, preferably 9 to ID). During the course of the dyeing operation the pH of the dye composition will sometimes change; therefore, in a preferred embodiment herein a buffer is included in the composition to maintain a relatively constant pH within the desired range. Any of the common peroxide-stable buffers suitable for use in the pH range from 8 to ll can be used herein for this purpose, e.g.,

carbonates, Na HPO NaH PO etc. Especially preferred herein are phosphate buffers, especially ortho-, meta-, and tri-polyphosphate salts. While any of the common buffers are useful herein, the phosphate buffer salts have the advantage that they are innocuous when applied to the skin, are efficient buffers over the pH range indicated, and stabilize the peroxide being used by preventing metal ion catalyzed peroxide decomposition. Buffers such as the phosphates are usually used at concentrations from about 0.1 percent to about 5 percent, by weight, in the present compositions. The carbonate or phosphate salts of arginine or the protamine proteins or polypeptides are self-buffering at the proper pH.

The dye precursors and color modifiers are known to be polymerized when contacted with liquid solutions of peroxides to form colored dye molecules. For this reason, it is necessary in the formulation of the dye compositions of this invention to exclude liquid peroxides therefrom until just prior to application of the compositions to the hair. This can be done, for example, by packaging the dye precursors, arginine or protamines and color modifiers separately from the peroxide; such separate packaging will be required when aqueous solutions of hydrogen peroxide (commercially available) are used herein. Alternatively, a dry peroxide source,

e.g., sodium peroxide, sodium perborate, ureaperoxide, and the like, can be admixed with the dye precursors, color modifiers, arginine, etc., buffer and the like in a dry packet. Such compositions are designed to be added to water or to a carrier liquid as hereinafter noted, just prior to use.

The coloring process of the present invention is preferably carried out in aqueous solution (the term solution" herein also encompasses fine dispersions or colloids of the reacting and reacted materials) but any liquid carrier medium which does not interfere with the coloring process and is safe for application to the skin can be used. When the dry compositions noted above are used, they are simply dispersed in the chosen carrier liquid by stirring or shaking. When aqueous hydrogen peroxide is used, the arginine or protamine, or salts thereof, dye precursors and color modifiers are simply admixed therewith. Examples of alternative solvents are glycerol, ethanol and formamide. The time of exposure of the hair to the coloring solution can be form a few seconds up to one or more hours but is preferably from about to 40 minutes.

It is recognized also that conventional hair coloring products contain thickeners such as carboxymethylcellulose, surfactants such as the nonylphenoxypolyoxyethylenes, and conditioners such as solubilized lanolin derivatives, and that such ingredients can also be utilized in the practice of the present invention.

In a preferred manner of carrying out the process of the present invention, an aqueous mixture is prepared containing 0.1 percent to 4.0 percent, by weight, of hydrogen peroxide and one or more oxidation dye precursors and optionally one or more color modifiers, the total weight percent of dye precursor in said mixture being from about 0.01 percent to about 2.0 percent. The pH of the mixture is adjusted with the arginine or protamine, and base as needed, and maintained throughout the coloring process within the range of about 8.0 to 11.0, preferably 9 to 10.0, by a suitable means such as by buffering with peroxide-compatible salts (e.g., a mixture of NaH PQ, and Na HPO The hair to be colored is immersed in the mixture. After the hair has reached the desired color, (normally in about 5 to 40 minutes) it is removed from the solution, rinsed and dried.

Alternatively, the arginine or protamine proteins and the dye precursors can be formulated together in a composition which can be diluted to the proper usage concentration immediately prior to use. Such compositions comprise the arginine or protamine compound and one or more oxidation dye precursors, and optionally one or more color modifiers. These compositions can be added directly to a buffered solution of hydrogen peroxide immediately before use. Although said compositions can contain only the arginine or protamine compounds, and dye precursor, they normally contain these materials in combination with an inert diluent in order to facilitate handling and measuring. The diluents can be a liquid such as water so as to form a liquid concentrate or they can be solids such as inorganic salts (e.g., sodium chloride, calcium sulfate, etc.) starches, sugars, etc. Normally the total amount of arginine or protamine compound and dye precursor in the compositions will be from about 0.5% to about 60 percent, by weight, the remainder of the composition comprising the diluent materials and optionally such other materials as hair conditioners (e.g., soluble lanolin de- EXAMPLE 1 Dry Hair Dye Composition Ingredient Weight K p-Phenylenediamine 0.2 Clupein carbonate 5.0 Sodium peroxide 2.0 Sodium carboxymethylcellulose 2.0

Balance Starch 50.0 g. of the above dry hair dye composition is added to an equivalent weight of water and mixed therewith to provide a dyeing solution comprising 0.1 percent p-phenylenediamine, 2.5 percent clupein carbonate, 1 percent sodium peroxide and 1 percent sodium carboxymethylcellulose. The composition has a pH of about 9. Light blond hair is coated with the thickened dyeing composition immediately after mixing and allowed to stand for about 25 minutes and is dyed a brown color. The dark brown dye is not substantially removed by shampooing.

In the above composition the p-phenylenediamine is replaced by an equivalent amount of ophenylenediamine, 2,4-toluenediamine, N,N-dimethylp-phenylenediamine, N-phenyl-p-phenylenediamine, 4-nitro-o-phenylenediamine, p-aminophenol, maminophenol, o-aminophenol, 2-nitro-p-aminophenol, N-methyl-p-aminophenol, 2-amino- 1 -phenol-4- sulfonic acid, p-methoxy-aniline, 2,5 dimethoxyaniline, p-hydroxyphenol, o-hydroxyphenol, 2-methoxyphenol, 4-methoxyphenol, 3-methoxy-4-hydroxybenzaldehyde, and 3,4-dihydroxybenzaldehyde, respectively, and equivalent hair dyes are secured. Hair dyed with these compositions achieves the colors noted in Table 1, below.

Table l Precursor Initial Precursor Conc. Hair Color Final Hair Color p-Phenylenediamine 0.1% light blond drab brown o-Phenylenediamine 0.l% light blond warm brown 2,4-Toluenediamine 0.l% light blond warm brown N,N-Dimethyl-p-phenyl- 0.l% light blond drab brown enediamine N-Phenyl-p-phenylene- 01% light blond black diamine 4-Nitro-o-phenylene 0.l% light brown warm brown diamine p-Aminophenol 0.l% light blond drab brown m-Aminophenol 0.l% light blond warm brown o-Aminophenol 0.l% light blond warm brown Z-Nitro-p-aminophenol 0.l% light brown warm brown N-Methyl-p-aminophenol 0.l% light blond gold blond 2-Amino-l-phenol-4- 0.l% light blond gold blond sulfonic acid 1 p-Methoxyaniline 0.l% light blond blue-gray 2,5-Dimethoxyaniline 0.l% light blond drab brown p-Hydroxyphenol 0.l% light blond drab blond o-Hydroxyphenol 0.l% light blond drab brown Z-Methoxyphenol 0.l% light blond gold blond 4-Methoxyphenol 0.l% light blond gold-red 3-Methoxy-4-Hydroxy- 0.l% light blond drab blond benzaldehyde 3,4-Dihydroxy- 0.l% light blond red benzaldehyde EXAMPLE 11 Dark Brown Hair Dye Ingredient Weight,%

p-Aminodiphenylamine 0.05 4-Amino-2-nitrophenol 0.10 p-Aminophenol 0.21 2-Nitro-p-phenylenediamine 0.01 p-Phenylenediarnine 2.1 1:1 Fusion mixture of 4-nitr0- o-phenylenediamine and 2 nitro-p-phenylenediamine 0.2 Pyrogallol 0.2 Resorcinol 1.4 Sodium sulfite 0.2 Arginine carbonate 20.0 Sodium peroxide 6.0 Sodium carboxymethylcellulose 4.0 Starch Balance The above dry dye composition is added to water (1:1 wt. basis) and mixed therewith to provide an odorless, thickened dyeing solution having a pH of about 9.3. Bleached blond hair is coated with said thickened dyeing solution immediately after mixing and allowed to stand for about 40 minutes and is dyed a dark brown color. The dark brown color is not substantially removed by shampooing.

1n the above composition the arginine carbonate is replaced by an equivalent amount of arginine phosphate, clupein carbonate, lacustrin carbonate, salmin carbonate, sperm nucleoprotein phosphate, iridin phosphate, macerated bovine testes nitrate, and gallin phosphate, respectively. The respective formulations are applied to bleached blond hair and dye said hair a dark brown color (-30 minutes) which is not substantially removed by shampooing.

The above dyeing composition is added to glycerol, ethyl alcohol, isopropanol, and 1:1 (wt.) mixtures thereof with water prior to application to the hair and equivalent results are secured.

The above compositions are adjusted to a pH about 11.0 using sodium hydroxide, and triethanolamine, respectively, and equivalent dyes are secured.

The above compositions are added to water at a weight ratio of dye composition to water of 1:3. The resulting hair dyes are applied to bleached hair and allowed to stand for about minutes and the hair is co]- ored a light brown color which is not substantially removed by shampooing.

EXAMPLE III Ash Blond Hair Dye -Continued Ash Blond Hair Dye Ingredient Weight,%

Sodium carboxymethylcellulose 4.0 Starch Balance The above composition is admixed with water (1:1 wt. basis) and applied to bleached hair for one hour; excess dye composition is removed form the hair by a water rinse and the hair dyed an ash blond color which is shampoo-stable.

In the above composition, each of the following modifications are made:

The sodium peroxide is replaced by an equivalent amount of urea-peroxide, peroxyacetic acid, pchloroperoxy-benzoic acid, and methylperoxyacetic acid, respectively, and equivalent results are secured in that the hair is dyed an ash blond color.

The above composition is added to water 1 :1 wt. basis) and adjusted to pH 8.0 with hydrochloric acid prior to application to the hair. The hair is dyed to an ash blond color in one hour.

The salmin carbonate is replaced by an equivalent amount of clupein, fontinin, salmin, iridin, lacustrin, gallin, sturin, sperm nucleoprotein, and macerated bovine testes, respectively, and the pH is adjusted with a sodium hydrogen phosphate buffer to 9.3 and equivalent compositions are secured.

The salmin carbonate is replaced by an equivalent amount of clupein carbonate, fontinin phosphate, salmin acetate, iridin chloroacetate, lacustrin fluoride, gallin lactate, sturin stearate, sperm nucleoprotein bicarbonate, and macerated bovine testes benzoate, respectively, and equivalent hair dyeing compositions are secured.

The p-aminodiphenylamine is replaced by 0- phenylenediamine, m-phenylenediamine, 4-amin0-2- nitrophenol, nitro-p-phenylenediamine, N-phenyl-pphenylenediamine, and 2,4-diaminoanisole, respectively, and equivalent results are secured.

The pyrogallol concentration is increased to 3.0 percent and the p-phenylenediamine concentration is increased to 1.6 percent and a purplish-black hair dye composition is thereby secured. This composition is mixed (1:1 wt.) with water and applied to the hair for a period of about 10 minutes and provides a purplishblack hair color which is substantially shampoo-stable.

Hair coloring products employing oxidation hair dyes are typically marketed in kit form, i.e., a package comprising an individually packaged oxidizing component and an individually packaged oxidation dyeing component. In an embodiment of this invention said oxidation component consists of an aqueous solution of a peroxide as detailed herein, most generally aqueous hydrogen peroxide having a concentration from about 0.1 percent to about 6 percent by weight, and said oxidation dyeing component comprises an oxidation dye precursor of the type hereinbefore detailed and an arginine or protamine compound or salt thereof, of the type hereinabove detailed. The components are mixed by the user immediately prior to application to the hair. An example of such kit is as follows:

A hair dyeing kit is assembled comprising a single package including therein: (1) a 4 oz. bottle of hydrogen peroxide (3 percent by weight H 0 and (2) a foil packet containing an oxidation dyeing component, said component consisting of 4 g. of p-phenylenediamine, 40 g. of arginine carbonate, 2 g. of sodium carboxymethylcellulose and 10 g. of starch. The oxidation dyeing component is admixed with the hydrogen peroxide and the solution is applied to the hair and provides a brown-black color which is substantially shampoostable.

In the above composition the arginine carbonate is replaced by an equivalent amount of arginine phosphate, clupein carbonate, clupein phosphate, salmin carbonate, and salmin phosphate, respectively, and equivalent results are secured.

In the above composition the 3 percent aqueous hydrogen peroxide solution is replaced by an equivalent volume of 0.1% hydrogen peroxide solution and equivalent results are secured.

In the above composition the arginine carbonate in the packet is replaced by 0.1 g. of arginine, 10 g. of clupein, 10 g. of salmin, l g. of iridin, 0.01 g. of sperm nucleoprotein and g. of lacustrin, respectively. 5 g. of a buffer (4 g. Na HPO ,1 g. of NaH PO is included in the packet in each case. The resulting coloring kits are used to dye hair.

In the above coloring kit the level of p phenylenediamine is reduced to 0.001 g. and a pale brown tint suitable for toning blond hair is secured.

What is claimed is:

l. A hair dye composition comprising: (1) from about 0.1 percent to about 20 percent by weight of a compound selected from the group consisting of urginine, a protamine protein, and a peroxide-compatible salt thereof; (2) from about 0.001 percent to about 6 percent by weight of one or more oxidation dye precursors; (3) from about 0.1 percent to about 6 percent by weight of a water-soluble peroxide compound and (4) an inert diluent.

2. A composition according to claim 1 wherein the protamine protein is selected from the group consisting of clupein fontinin, salmin, iridin, lacustrin, gallin, sturin, sperm nucleoprotein derived from mollusks (Patella coerulea), macerated bovine testes, and a peroxide-compatible salt thereof.

3. A composition accordng to claim 1 wherein the dye precursor is selected from the group consisting of compounds having the formula R N R wherein Y is selected from the group consisting of hydrogen, halogen, nitro, amino, hydroxyl,

O 0 II II CH COM and SO M where M is hydrogen, alkali or alkaline earth metal, ammonium or substituted ammonium wherein one or more hydrogens on the ammonium ion is replaced with a l to 3 carbon atom alkyl or hydroxyalkyl radical, R R R and R are the same or different from each other and are selected from the group consisting of hydrogen, C to C alkyl and alkenyl and C to C aryl, alkaryl, and aralkyl, R is selected from the group consisting of hydrogen, C to C unsubstituted or substituted alkyl and alkenyl wherein the substituents are selected from those designated as Y, and C to C unsubstituted or substituted aryl, alkaryl and aralkyl wherein the substituents are selected from those designated as Y, and R is selected from the group consisting of hydrogen, and C to C substituted or unsubstituted alkyl and alkenyl wherein the substituents are those defined as Y, and a peroxide-compatible salt thereof.

4. A composition according to claim 1 wherein the oxidation dye precursor is selected from the group consisting of pyrogallol, resorcinol, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, oaminophenol, p-aminophenol, 4-amino-2nitrophenol, nitro-p-phenylenediamine, N-phenyl-pphenylenediamine and 2,4-diminoanisole.

5. A composition according to claim I also containing from about 0.00l percent to about 6 percent by weight of a color modifier selected from the group consisting of an aromatic amine and a phenolic compound.

6. A composition according to claim 1 wherein the water-soluble peroxide is selected from the group consisting of hydrogen peroxide, an alkali metal peroxide and urea-peroxide.

7. A composition according to claim 1 also containing from about 0.1 percent to about 5 percent by weight of a peroxide-stable buffer capable of maintaining a pH of from about 8 to about ll in aqueous solution.

8. A hair dye composition comprising: (1) from about 0.5 percent to about 4 percent by weight of a compound selected from the group consisting of arginine carbonate, arginie chloride, arginine phosphate, clupein carbonate and salmin phosphate; (2) from about 0.01 percent to about 2 percent by weight of an oxidation dye precursor selected from the group consisting of pyrogallol, resorcinol, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, oaminophenol, p-aminophenol, 4-amino-2-nitrophenol, nitro-p-phenylenediamine, N-phenyl-pphenylenediamine and 2,4-diaminoanisole; (3) from about 0.1 percent to about 6 percent by weight of a water-soluble peroxide compound selected from the group consisting of hydrogen peroxide, an alkali metal peroxide and urea-peroxide and (4) an inert diluent.

9. A hair dye composition comprising: (1) from about 0.1 percent to about 20 percent by weight of a compound selected from the group consisting of arinine carbonate, arginine chloride and arginine phosphate; (2) from about 0.001 percent to about 6 percent by weight of one or more oxidation dye precursors; (3) from about 0.1 percent to about 6 percent by weight of a water-soluble peroxide compound and (4) an inert diluent.

10. A process for dyeing hair comprising applying to said hair a dyeing composition comprising an aqueous solution of 1) from about 0.1 percent to about 20 percent by weight of a compound selected from the group consisting of arginine, a protamine protein, and a peroxide-compatible salt thereof; (2) from about 0.001 percent to about 6 percent by weight of one or more oxidation dye precursors; and (3) from about 0.1 to about 6 percent by weight of a water-soluble peroxide compound, said composition having a pH from about 8 to about 1 l, and being applied in an amount and for a time sufficient to yield the desired color.

11. Aprocess according to claim 10 wherein the arginine compound is selected from the group consisting of arginine carbonate, arginine chloride and arginine phosphate.

12. A process according to claim 10 wherein the protamine protein is selected from the group consisting of clupein, fontinin, salmin, iridin, lacustrin, gallin, sturin, sperm nucleoprotein derived from mollusks (Patella coerulea), macerated bovine testes, and a peroxide-compatible salt thereof.

13. A process according to claim 10 wherein the oxidation dye precursor is selected from the group consisting of compounds having the formula R N R and , O I ll CH ll C-OM and SO M where M is hydrogen, alkali or alkaline earth metal, ammonium or substituted ammonium wherein one or more hydrogens on the ammonium ion is replaced with a 1 to 3 carbon atom alkyl or hydroxyalkyl radical, R R R 'and R are the same or different from each other and are selected from the group consisting of hydrogen C, to C alkyl and alkenyl and C to C aryl, alkaryl, and aralkyl, R is selected from the group consisting of hydrogen, C, to C unsubstituted or substituted alkyl and alkenyl wherein the substituents are selected from those designated as Y, and C to C unsubstituted or substituted aryl, alkaryl and aralkyl wherein the substituents are selected from those designated as Y, and R is selected from the group consisting of hydrogen, and C, to C substituted or unsubstituted alkyl and alkenyl wherein the substituents are those defined as Y, and a peroxide-compatible salt thereof.

16. A process according to claim 10 wherein the water-soluble peroxide is selected from the group consisting of hydrogen peroxide, an alkali metal peroxide and urea-peroxide. 

2. A composition according to claim 1 wherein the protamine protein is selected from the group consisting of clupein fontinin, salmin, iridin, lacustrin, gallin, sturin, sperm nucleoprotein derived from mollusks (Patella coerulea), macerated bovine testes, and a peroxide-compatible salt thereof.
 3. A composition accordng to claim 1 wherein the dye precursor is selected from the group consisting of compounds having the formula
 4. A composition according to claim 1 wherein the oxidation dye precursor is selected from the group consisting of pyrogallol, resorcinol, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, o-aminophenol, p-aminophenol, 4-amino-2nitrophenol, nitro-p-phenylenediamine, N-phenyl-p-phenylenediamine and 2,4-diminoanisole.
 5. A composition according to claim 1 also containing from about 0.001 percent to about 6 percent by weight of a color modifier selected from the group consisting of an aromatic amine and a phenolic compound.
 6. A composition according to claim 1 wherein the water-soluble peroxide is selected from the group consisting of hydrogen peroxide, an alkali metal peroxide and urea-peroxide.
 7. A composition according to claim 1 also containing from about 0.1 percent to about 5 percent by weight of a peroxide-stable buffer capable of maintaining a pH of from about 8 to about 11 in aqueous solution.
 8. A hair dye composition comprising: (1) from about 0.5 percent to about 4 percent by weight of a compound selected from the group consisting of arginine carbonate, arginie chloride, arginine phosphate, clupein carbonate and salmin phosphate; (2) from about 0.01 percent to about 2 percent by weight of an oxidation dye precursor selected from the group consisting of pyrogallol, resorcinol, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, o-aminophenol, p-aminophenol, 4-amino-2-nitrophenol, nitro-P-phenylenediamine, N-phenyl-p-phenylenediamine and 2,4-diaminoanisole; (3) from about 0.1 percent to about 6 percent by weight of a water-soluble peroxide compound selected from the group consisting of hydrogen peroxide, an alkali metal peroxide and urea-peroxide and (4) an inert diluent.
 9. A hair dye composition comprising: (1) from about 0.1 percent to about 20 percent by weight of a compound selected from the group consisting of arinine carbonate, arginine chloride and arginine phosphate; (2) from about 0.001 percent to about 6 percent by weight of one or more oxidation dye precursors; (3) from about 0.1 percent to about 6 percent by weight of a water-soluble peroxide compound and (4) an inert diluent.
 10. A process for dyeing hair comprising applying to said hair a dyeing composition comprising an aqueous solution of (1) from about 0.1 percent to about 20 percent by weight of a compound selected from the group consisting of arginine, a protamine protein, and a peroxide-compatible salt thereof; (2) from about 0.001 percent to about 6 percent by weight of one or more oxidation dye precursors; and (3) from about 0.1 to about 6 percent by weight of a water-soluble peroxide compound, said composition having a pH from about 8 to about 11, and being applied in an amount and for a time sufficient to yield the desired color.
 11. A process according to claim 10 wherein the arginine compound is selected from the group consisting of arginine carbonate, arginine chloride and arginine phosphate.
 12. A process according to claim 10 wherein the protamine protein is selected from the group consisting of clupein, fontinin, salmin, iridin, lacustrin, gallin, sturin, sperm nucleoprotein derived from mollusks (Patella coerulea), macerated bovine testes, and a peroxide-compatible salt thereof.
 13. A process according to claim 10 wherein the oxidation dye precursor is selected from the group consisting of compounds having the formula
 14. A process according to claim 10 wherein the oxidation dye precursor is selected from the group consisting of pyrogallol, resorcinol, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, o-aminophenol, p-aminophenol, 4-amino-2-nitrophenol, nitro-p-phenylenediamine, N-phenyl-p-phenylenediamine and 2,4-diaminoanisole.
 15. A process according to claim 10 wherein the dyeing composition also contains from about 0.001 percent to about 6 percent by weight of a color modifier selected from the group consisting of an aromatic amine and a phenolic compound.
 16. A process according to claim 10 wherein the water-soluble peroxide is selected from the group consisTing of hydrogen peroxide, an alkali metal peroxide and urea-peroxide. 